Hydrogen purification process and system

ABSTRACT

A hydrogen generation system is disclosed that includes a fuel reforming reactor generating a hydrogen-rich reformate gas at a temperature greater than 150 C, a pressure swing adsorption (PSA) hydrogen purification unit that separates the reformate gas into a relatively pure hydrogen stream and an off-gas stream, and a catalytic reactor down stream of the PSA unit that converts carbon monoxide (CO) and hydrogen (H 2 ) contained in the relatively pure hydrogen stream into methane (CH 4 ) and water vapor (H 2 O). The method of purification involves generating a hydrogen-rich reformate gas at a temperature greater than 150 C in a fuel reforming reactor, separating the reformate gas into a relatively pure hydrogen stream and an off-gas stream in a pressure swing adsorption (PSA) hydrogen purification unit, and converting carbon monoxide (CO) and hydrogen (H 2 ) contained in the relatively pure hydrogen stream into methane (CH 4 ) and water vapor (H 2 O) in a catalytic reactor down stream of the PSA unit. The hydrogen can be further purified by including a secondary purification stage downstream of the PSA unit and the catalytic reactor wherein the secondary purification stage has a water adsorbent material bed that adsorbs the water vapor H 2 O and a hydrogen absorbent material downstream of the water absorbent material that absorbs hydrogen gas preferentially, thus concentrating the non-hydrogen components, such as CH 4 , into an exhaust stream that exits the bed, wherein the absorbed hydrogen gas is then desorbed to create an exiting very pure hydrogen stream.

RELATED APPLICATION

This application claims the benefit of and priority to U.S. ProvisionalApplication Ser. No. 60/781,616, filed Mar. 10, 2006, the contents ofwhich are incorporated by reference herein in its entirety.

BACKGROUND

1. Field

This disclosure relates to improving the purity of hydrogen gas using asecondary hydrogen purification method downstream of a primary hydrogenpressure swing adsorption unit.

2. General Background

A hydrogen generation unit (HGU) is a combination of thermo-chemicalprocesses that convert a fuel-steam mixture into a hydrogen-rich gasmixture typically composed of hydrogen (H₂), carbon monoxide (CO),carbon dioxide (CO₂), methane (CH₄), water vapor (H₂O) and other gasesdepending on the composition of the fuel feedstock. Typically thismixture is known as reformate. For many applications this reformatestream is then passed to a hydrogen purification unit in which 60% to90% of the hydrogen is separated into a relatively pure hydrogen stream(99+% H₂) and an off-gas stream consisting of the other species in thereformate mixture. One typical method used to purify the reformate is apressure swing adsorption (PSA) unit, which consists of a series of bedfilled with adsorbent material (typically but not limited to zeolites).As the pressurized reformate flows through the bed gaseous speciesadsorb on to the active surfaces. Since the H₂ is the least stronglyadsorbed species in the reformate stream, a pure H₂ gas exits the bed.After a period of time when the adsorbent sites begin to becomesaturated, the feed gas is removed and the bed is depressurized forcingthe adsorbed species to desorb and exit the bed as the off-gas stream.By cycling several beds through this pressurization and depressurizationcycle a continuous H₂ purification process is created. As the capacitiesof the beds are pushed to their limits with higher flow rates and fastercycle times, non-hydrogen gas species begin to contaminate therelatively pure H₂ gas stream. Typically, the species of concern are theother gases in the reformate stream such as CH₄, CO, and CO₂.

Of the non-hydrogen species typically in the reformate feed to the PSA,H₂O and CO₂ are strongly adsorbed onto the surfaces of the zeolites andCO and CH₄ are weakly adsorbed. As a result the relatively pure hydrogenstream exiting the PSA typically has CO and CH₄ as the primarycontaminates. In fuel cell and hydrogen refueling station applicationsthe most critical of these contaminates is the CO, because is causesperformance degradation of the fuel cell or metal hydride hydrogenstorage units. CH₄ is relatively non-reactive in the fuel cell and metalhydride materials, and therefore, does not cause performancedegradation. It is beneficial to include a reactor between the PSA andthe fuel cell that converts the CO back into CH₄. This reactor allowsthe capacity of the PSA to be increased substantially without impactingperformance of fuel cell units downstream.

One reaction mechanism that achieves this is known as methanation, whichis the reverse of the steam reforming reactions. Typically inmethanation reactors, a catalyst is used and ruthenium based catalystshave proven to be very effective, although other catalysts such asnickel, platinum, etc. can be used. For these catalysts to be effectivethe temperature of the catalyst must be greater than 150 C andpreferably greater than 190 C.CO+3H₂→CH4+H₂O+Heat E-1 PrimaryCO₂+4H₂→CH4+2H₂O+Heat E-2 Secondary

Methanation reactors have been integrated into hydrogen generationsystems in the prior art, but typically they have been used upstream ofthe PSA unit to minimize the CO concentration entering the PSA unit.Typically, this upstream location is used because the reformate gas isat the appropriate temperature range to maintain the catalyst activity.One issue with this art is the secondary reaction identified above,where CO₂ is also converted into CH₄ since the CO₂ concentration istypically 20% in comparison to CO concentrations in the 2 to 4% range.To manage the methanation reaction a tight temperature range ispreferably maintained in the catalytic bed which promotes the reactionof CO but does not promote the reaction of the secondary reaction withCO₂. Not only is this a source of process inefficiency, but it can alsoresult in thermal run-away in which all the CO₂ is reconverted back intoCH₄. Therefore a system and method are needed which alleviates theseinefficiencies and precludes thermal run-away from occurring.

SUMMARY OF THE DISCLOSURE

The present disclosure is directed to a hydrogen generation system andmethod that fundamentally includes operations of generating ahydrogen-rich reformate gas at a temperature greater than 150 C in afuel reforming reactor, separating the reformate gas into a relativelypure hydrogen stream and an off-gas stream in a pressure swingadsorption (PSA) hydrogen purification unit, and converting low levelconcentrations of carbon monoxide (CO) contained in the relatively purehydrogen stream into methane (CH₄) and water vapor (H₂O) in a catalyticreactor down stream of the PSA unit. Preferably the hydrogen generationmethod also includes positioning the catalytic reactor such that thetemperature of the hydrogen-rich reformate gas maintains the temperatureof the catalytic reactor.

Alternatively, or, in addition, the hydrogen generation system andmethod includes integrating the fuel reforming reactor with a combustionreactor that uses the off-gas stream to provide thermal energy to thefuel reforming reactor. Here the combustion reactor has a combustionexhaust gas at a temperature greater than 150 C, and includespositioning the catalytic reactor such that the temperature of theexhaust gas maintains the temperature of the catalytic reactor.

The hydrogen generation method and system may include a secondarypurification stage downstream of the PSA unit and the catalytic reactor.The secondary purification stage has a water adsorbent material bed thatadsorbs the H₂O vapor; and concentrates non-hydrogen components into anexhaust stream exiting the bed by providing a hydrogen absorbent (oradsorbent) material downstream of the water absorbent material bed.Finally, the absorbed hydrogen gas is desorbed to generate a very purehydrogen stream.

The above-mentioned features and objects of the present disclosure willbecome more apparent with reference to the following description takenin conjunction with the accompanying drawings.

DRAWINGS

FIG. 1 illustrates one embodiment of a system of the disclosure in whichthermal energy of the reformate stream is used to maintain the catalystat optimum conditions.

FIG. 2 illustrates a second embodiment of the system in which thermalenergy of the combustion exhaust gas is used to maintain the catalyst atoptimum conditions.

FIG. 3 is a graph that illustrates test data collected on a hydrogengeneration unit shown in FIG. 1.

FIG. 4 illustrates an exemplary system in which a secondary hydrogenpurification process is added downstream of the methanation reactor ineither of the systems shown in FIG. 1 or 2.

FIG. 5 is a set of tables showing predicted hydrogen production levelsat various stages in the systems shown in FIGS. 1, 2, and 4.

FIG. 6 is a graph of critical CO conversion and hydrogen purity in thepurification process shown in FIG. 4.

DETAILED DESCRIPTION

FIG. 1 illustrated one exemplary embodiment of a system in accordancewith the disclosure in which a methanation reactor is integrated into asystem based on steam reformation and PSA purification. Basically themethanation reactor is integrated into the system such that thereformate gas stream exiting the water gas shift (WGS) reactor at atemperature greater than 150 C is used as the thermal energy source tomaintain the methanation reactor at its optimum temperature. Typicallythe exit temperature of the WGS exit stream is in the range of 150 C to400 C, and more preferably in the range of 200 C to 300 C.

The embodiment shown in FIG. 2 is similar to that of FIG. 1 except thatcombustion exhaust gas is used to maintain temperature in themethanation reactor. Both of these embodiments provide the uniqueadvantage of the disclosure that places the methanation reactordownstream of the PSA. Since most if not all the CO₂ is removed from therelatively pure hydrogen product stream from the PSA, there is no needfor tight temperature control because the concentration of reactants (COand CO₂) are relatively low (typically below 1000 ppm) and thepurification goal is to convert all these reactant species into CH₄.Therefore, there is no upper limit to the catalytic reactor'stemperature, because the concentration of CO₂ in the relatively purehydrogen stream is insufficient to allow thermal runway of themethanation reactor.

Now specific reference is made to the first embodiment of the systemshown in FIG. 1. This embodiment of the hydrogen generation system 100consists of a reformer 102, WGS reactor 103, condenser 104, PSA 105,methanation reactor 106, and hydrogen gas recuperative heat exchanger107. The reformer 102 has an integrated combustor section and steamreforming section (not detailed). Each reactor section or process in thereformer 102 has an optimum temperature range based on the specificcatalysts and processes that are occurring.

The combustion section receiving air 112 and PSA off gas 123 which istypically 40 to 60% hydrogen reacts this fuel air mixture generatingheat and operating at a temperature in the 700 to 950 C range. Thereformer 102 typically operates in the 650 to 900 C range or at atemperature 50 to 100 C cooler than the combustion section within thereformer 102 to promote the transfer of heat from the combustion sectionto the reformation section. The WGS typically operates in the 500 to 250C range depending on the specific catalysts. The PSA's temperature rangeis typically in the 40 to 80 C range, and requires no liquid water inthe feed. Therefore the condenser 104 is used to cool and dry thereformate stream 136 and can include a reheat function to ensure thatthe reformate stream 115 entering the PSA 105 has a dew point less thanthe dry bulb temperature. The ideal methanation reactor temperature isabove 190 C. Since the PSA operating temperature is typically lower thanthe methanation temperature, methanation reactors are typically notutilized downstream of the PSA.

Fuel 110 and water vapor or steam 111 enters the steam reforming sectionof the reformer 102 where the steam-fuel mixture is converted into apre-WGS reformate stream 113 containing H₂, CO, CO₂, H₂O, CH₄, and othertrace species. This stream 113 enters the WGS 103 where additional CO isreacted with H₂O to form H₂ and CO₂ creating the reformate stream 135that exits the WGS 103. In some alternative embodiments the reformer 102and WGS 103 can be integrated into a single assembly, and in others theWGS can be minimized or even eliminated. The thermal energy contained inthe reformate stream 135 is used to heat the methanation reactor 106 byindirect transfer from heat exchanger surface 132 to methanationcatalyst 131. The reformate steam 136 flows to the condenser 104 inwhich thermal energy is removed to manage the inlet PSA 105 temperatureand to condenser water from the reformate mixture. The condensate water122 is removed. The drier reformate gas 115 is passed to the PSA 105 inwhich it is separated into a relatively pure hydrogen stream 116 and anoff-gas stream 123.

The relatively pure hydrogen stream 116 is raised in temperature by therecuperative heat exchanger 107. The temperature of the relatively purehydrogen stream 116 is dependant on the sizing and configuration of therecuperative heat exchanger 107, but typically temperatures in the 100 Cto 150 C are achievable depending on the temperature of the methanationreactor. The hotter relatively pure hydrogen stream 117 then enters themethanation reactor 106 in which any CO and CO₂ contaminates are reactedwith H₂ to form CH₄ and H₂O. The temperature of the methanation reactor106 is managed by the indirect heat transfer with the reformate stream135 and the heat exchange surface 132. Although the methanationreactions (E-1 and E-2) are exothermic, the heat generated is notsufficient to control the temperature of the methanation reactor 106because the concentrations of CO and CO₂ in the feed stream 117 arerelatively low, typically less than 1000 ppm or 0.1%. The low COconcentration, relatively pure hydrogen stream 118 exits the methanationreactor 106 and provides thermal energy to the recuperative heatexchanger 107. Typically the temperature of the exit hydrogen stream 119is in the range of 100 to 160 C depending on the surface area and designof heat exchanger 107.

The advantage of this system 100 and the method of its operation is toproduce a relatively pure hydrogen exit stream 119 in which the onlyimpurities are CH₄, H₂O and other non-reactive species, such asnitrogen, argon, etc. The reactive species CO and CO₂ have beenconverted back into CH₄, which is non-reactive at the operatingtemperatures of a proton exchange membrane (PEM) fuel cell. Thisrelatively pure hydrogen exit stream 119, for example, can be sentdirectly to a PEM fuel cell for power generation. The PEM fuel cellconsumes the hydrogen to generate power and the CH₄ and othernon-reactive species will build up concentration in the dead headed flowpath. Periodically a valve will open forcing the collected CH₄ and othernon-reactive species out of the fuel cell to maintain performance whileachieve 99% hydrogen utilization in the fuel cell.

FIG. 2 illustrates a second embodiment 200 of the system in accordancewith the present disclosure. In this embodiment 200 like numbers areused as in FIG. 1 for the same components. Embodiment 200 differsspecifically from system 100 in that exhaust gas 120 from the reformer102 feeds directly into and through the heat exchanger surface 132rather than the discharge of the WGS 103 feeding the heat exchanger 132.Thus the thermal energy used to maintain the temperature of themethanation reactor 106 is energy from the exhaust gas 120 from thecombustion section of the reformer 102. Since this temperature source isused, the reformate stream 214 from the WGS 103 flows directly into thecondenser 104. The combustion exhaust 120 from the reformer 102 istypically used for feed air 112 preheating and exits the reformer 102 inthe temperature range of 150 to 300 C depending on the preheatingcharacteristics.

FIG. 3 illustrated actual test data graph 300 collected from a HGU witha methanation reactor in accordance with the present disclosure. The HGUwas an integrated steam reformer and water gas shift reactor system 100as illustrated in FIG. 1. The reformate gas 135 was used to provide thethermal energy for the methanation reactor 106 prior to flowing to thecondenser 104 and the PSA unit 105. The CO and CH₄ concentration afterthe PSA unit 105 and after the methanation reactor 106 are plotted. Therelatively pure hydrogen stream 119 exiting the test hardware had a COconcentration of less than 0.5 ppm as illustrated by the open squaredata set 341 and a CH₄ concentration as illustrated by the downwardlypointed open triangle data set 344. Both data sets are plotted withhydrogen purity as the x-axis. The open circle data set 342 illustratesthe CO concentration in stream 116 exiting the PSA 105 and the upwardlypointed open triangle data set 343 illustrates the CH₄ concentration instream 116. This data set indicates the increase in CH₄ concentrationafter the methanation reactor 106 which corresponds to the decrease inCO concentration.

In some refueling station and industrial gas applications a purehydrogen product of greater than 99.9% is required. To achieve thislevel of purity, typically the PSA unit is increased in size and thehydrogen recover in the PSA unit is decreased until there are very fewnon-hydrogen species in the PSA product gas 116. A hydrogenconcentration of 99.99+% is equivalent to less than 100 ppm non-hydrogenconcentration and a 99.999+% is equivalent to less than 10 ppmnon-hydrogen concentration. This requirement can force the PSA unit 105to be large and costly.

The systems 100 and 200 illustrated in FIG. 1 and FIG. 2 can also beused in these applications with an additional secondary purificationsystem 400 positioned downstream of the relatively pure hydrogen exitstream 119. The secondary purification system 400 allows the primary PSAunit 105 to be decreased in size and cost and operated at a faster cycletime, which also helps decrease pressure pulsations in both the off-gasand product gas. The secondary purification subsystem 400 is illustratedin FIG. 4.

The objective of subsystem 400 is to purify the reformate stream with aPSA unit 105 allowing CH₄, CO, and CO₂ as contaminates at concentrationsless the 0.1% or 1000 ppm. This allows the PSA unit 105 to beconsiderably downsized and a very rapid cycle can be used to maximizethe capacity of the PSA unit 105. Downstream of the PSA unit 105 amethanation reactor 106 as indicated in FIG. 1 or 2 is used to convertthe CO and CO₂ into additional CH₄ and H₂O. Downstream of themethanation reactor 106 this hydrogen stream is cooled and passedthrough a desiccant material to remove the water vapor produced in themethanation reactor 106. This dry stream is then passed into a H₂absorbent bed such as a metal hydride in which the H₂ is absorbed intothe material and stored for later release.

Removal of the water vapor and CO is important in this secondarypurification subsystem 400, because these species can damage theperformance and endurance of the metal hydride bed. The absorbent bed isdesigned to have a high length over width ratio such that as thehydrogen gas is adsorbed the CH₄ and other non-reactive, non-condensablespecies are concentrated as they move down the bed. Finally, the gasesexit the bed as a hydrogen-rich mixture with higher concentrations ofCH₄ and other non-reactive species. These gases are vented from thesecondary purification system 400 and may be returned to the combustionsection of the reformer 102. Valves in the system 400 are used toisolate the beds and to open the H₂ absorbent to the product H₂ supplyline. The absorbed H₂ is desorbed resulting in a very pure H₂ stream,typically in the 99.995+% range because the only non-hydrogen is thecontaminate CH₄ and other non-reactive, non-condensable species in thegas volume around the absorbent material.

In reference to FIG. 4 one embodiment of the secondary hydrogenpurification system 400 consists of four beds, first desiccant bed 401,first H₂ absorbent bed 402, second desiccant bed 403 and second H₂absorbent bed 404. The system 400 also has a series of valves thatmanage the flow of relatively pure hydrogen stream from the methanationreactor 106 and feed line 440 to the product hydrogen supply line 442and the vent line 441. In this embodiment first and second parallelpaths 408 and 409 are illustrated which cycle on and off in sequence tocreate a continuous process. Other embodiments may include three or moreparallel paths to optimize purity and process integration. The openvalves of the first parallel path 408 are shown as white or opensymbols, while the closed valves of the second parallel path 409 areshown as dark or solid symbols. The valves are shown as on-off solenoidvalves, but could also be rotary valve assemblies similar to the valvesused in a rapid cycle PSA unit. Rotary valves assemblies provideadvantages of reliability, lower cost, and simple process control.

Process gases from the methanation reactor 106 flow into the system 400through supply line 440. In FIG. 4 the first parallel path 408 supplyvalve 431 is open allowing the hot gas from the methanation reactor 106to enter the first heat exchanger coil 410 of first desiccant bed 401,while second parallel path supply valve 451 is closed. The hot gas fromthe methanation reactor 106 transfers heat to the desiccant material 412of desiccant bed 401. The gas flows from coil 410 to second heattransfer coil 411 embedded in first H₂ absorbent bed 402 againtransferring heat to the first H₂ absorbent material 413. Absorbed H₂from the prior cycle in the first material 413 is desorbed and flowsthrough open first exit valve 436 and out of the system through productline 442.

H₂ desorption is endothermic which decreases the temperature of thefirst absorbent material 413 and helps transfer heat from second coil411 cooling the gas temperature in coil 411. The gas flows from thesecond coil 411 through open valve 132 and into second desiccant bed 403and past the second desiccant material 462 which adsorbs any water vaporin the gas stream generated by the methanation reactions in bed 106. Thedry hydrogen rich gas flows through open valve 433 and into second H₂absorbent bed 404 and H₂ absorbent material 463. The hydrogen in thestream is absorbed as the gas flow through second absorbent bed 463thereby increasing the concentration of CH₄ and other non-reactivespecies in the process flow. This gas then exits the second H₂ absorbentbed 404 through open valve 434 and into first desiccant bed 401 incontact with first desiccant material 412. The heat transferred fromfirst coil 410 causes the adsorbed water vapor in first desiccantmaterial 412 to evolve and flow out of the system through open valve 435to system vent 441.

Once the second desiccant material 462 or the second absorbent material463 nears saturation the process cycle is reversed and flow is divertedthrough the second parallel path 409 by closing the open valves 431,432, 433, 434, 435, and 436 and opening the closed valves 451, 452, 453,454, 455, and 456. When the secondary parallel path 409 is active, heattransferred in third coil 457 and fourth coil 458, while water vapor isadsorbed in first desiccant material 412 and hydrogen is absorbed infirst absorbent material 413. Similarly, product hydrogen is desorbedfrom second absorbent material 463 flowing through valve 456 towardproduct line 442.

In one embodiment of the secondary purification system 400 the hydrogenabsorbent material 413 and 463 is a metal hydride type material. Thematerial absorbs H₂ molecules into the metal lattices and has thecapacity to absorb approximately 150 to 300 times the volume of hydrogenat standard conditions in comparison to the volume of metal. Anyabsorbent or adsorbent materials can be used which preferentially removeH₂ gas from a mixture.

The method described is very simple in that all the open valves areclosed and all the closed valves are open uniformly. More complex andpotentially more effective cycles are embodied. For example the purgevalve 434 positioned between the second H₂ absorbent material 463 andthe first desiccant material 412 can be opened after the starting theprocess parallel path 408, to maintain the pressure of the process gasesin absorbent material 463 and thereby, enhance the percentage of theprocess hydrogen gas in the flow stream that is absorbed in the material463.

Similarly, the open valves of parallel path 408 can be closed except forpurge valve 434 and exhaust valve 435 which are left open to allow abrief period during which process gases in the gas volumes of absorbentmaterial 463 are purged due to depressurization and desorption of purehydrogen. The pure hydrogen pushes any process gas with contaminates outthrough valve 434. After the brief period parallel path 463 valves areclosed and process flow is initiated through parallel path 409. As aresult the hydrogen gas allowed to flow through product valves 436 and456 is extremely pure achieving purities one magnitude greater thanwithout this delay.

An analytical model was developed to assess the performancecharacteristics and sensitivities of the process to the variousparameters. One set of results from this model is shown in FIG. 5. ThisFIG. 5 is divided into six blocks of data. The first block (Table 5.A)shows a typical reformate composition entering the PSA primary hydrogenpurification unit. The analysis was conducted for one multiple of 100moles at this point, and the concentrations of gas species are shown inppm and percent in the third and fourth column of each block of data,respectively.

The second block (Table 5.B) illustrates an assumed relatively purehydrogen stream 116 leaving the primary purification unit 105 as inFIG. 1. Assuming that 70% of the hydrogen was recovered, the COconcentration was set at 200 ppm and the CH₄ concentration was set at800 ppm, with 10 ppm of CO₂ and 3 ppm or other non-reactive species suchas argon or nitrogen. This composition is representative of therelatively pure hydrogen stream 116. Assuming the initial 100 moles ofgas and 74 moles of H₂ the relatively pure hydrogen stream has 51.8moles of H₂ at the 70% recovery rate. The hydrogen purity of this streamis only 99.899%, which is acceptable for a fuel cell from a bulkcharacteristic except for the 200 ppm of CO which would degrade PEM fuelcell performance very rapidly.

To address this issue a methanation reactor 106 is integrated into thesystem (FIG. 1 or 2). The methanation reaction converts 99.975% of theCO and CO₂ into CH₄ and H₂O and the outlet conditions are shown in thethird block of data (Table 5.C). The H₂ concentration has decreasedslightly because of the H₂ losses, but the output of the methanationreactor 106 is acceptable for direct fuel cell consumption because theCO concentration is 0.05 ppm well below the required 1 ppm level.Actually if only 99.5% of the CO is converted in the methanationreaction the CO concentration would be 1 ppm in the outlet.

The water content after the methanation reaction is 220 ppm, and becausethe assumed H₂ absorbent is a metal hydride, this concentration of waterwould damage the hydride. The desiccant material removes this water in aprocess assumed to be 99.99% effective as shown (Table 5.D). As the gasstream flow through the hydride, H₂ is absorbed. If 95% of the hydrogenis absorbed, the outlet concentration of CH₄ and CO has increased asshown (Table 5.E). The CO level is still approximately 1 ppm and the CH₄concentration has increased from 1010 ppm to 19830 ppm or just under 2%.Since only 95% of the hydrogen is absorbed, the hydrogen concentrationis still 98% and 2.59 moles of H₂ leave the secondary system with theCH₄ and CO. The 49.18 moles of H₂ absorbed results in the net H₂recovery being 66.5% (94.9% of the initial 70% value). Assuming that themetal hydride had only a 150 times H₂ gas volume to vessel volume, whenthe desorbed H2 during the next parallel path cycle this volume of H₂ ismixed with one volume of absorbent bed inlet gas (with 1010 ppm CH₄ andH₂ concentration of 99.9%). The result is an H₂ purity of 99.9993% afterthe secondary purification process as shown (Table 5.F).

One aspect of the durability of the secondary purification process 400is the concentration of CO at the end of the H₂ absorbent beds 413 or463 as the H₂ is absorbed. An example of this analysis is presented inFIG. 6 illustrating the CO concentration at the end of the absorptionbed as a function of the percent of H₂ recovered in the secondary bed(x-axis) and the level of CO conversion in the methanation reactor 106.With decreased activity in the methanation reactor (106) the H₂ recoveryin the secondary purification process 100 must be decreased to maintainCO concentrations at an acceptable level. If H₂ absorbent materials 413and 463 with higher tolerance to CO are used optimization of theseparameters can be adjusted. Higher activity of the methanation reactor106 is achieved by increasing the temperature of the catalyst. Theinnovations defined in FIGS. 1 and 2 are needed to passively achievereactor 106 temperatures without too much system complexity or processinefficiencies.

While the apparatus and method have been described in terms of what arepresently considered to be the most practical and preferred embodiments,it is to be understood that the disclosure need not be limited to thedisclosed embodiments. It is intended to cover various modifications andsimilar arrangements included within the spirit and scope of the claims,the scope of which should be accorded the broadest interpretation so asto encompass all such modifications and similar structures. The presentdisclosure includes any and all embodiments of the following claims.

1. A hydrogen generation method comprising: generating a hydrogen-richreformate gas at a temperature greater than 150 C. in a fuel reformingreactor; separating the reformate gas into a relatively pure hydrogenstream and an off-gas stream in a pressure swing adsorption (PSA)hydrogen purification unit, and converting carbon monoxide (CO) and atleast a portion of hydrogen (H₂) contained in the relatively purehydrogen stream into methane (CH₄) and water vapor (H₂O) in a catalyticreactor down stream of the PSA unit; providing a first secondarypurification stage downstream of the PSA unit and the catalytic reactor,the first secondary purification stage having a water adsorbent materialbed that adsorbs the H₂O; and a hydrogen absorbent (or adsorbent)material bed downstream of the water adsorbent material bed;concentrating the hydrogen into the hydrogen absorbent material bed;providing a second secondary purification stage downstream of the PSAunit and the catalytic reactor connected in parallel to the firstsecondary purification stage, the second secondary purification stagehaving a second water adsorbent material bed that that adsorbs the H20followed by a second hydrogen absorbent material bed; and switching flowof the relatively pure hydrogen stream to the second secondarypurification stage while desorbing the absorbed hydrogen gas from thefirst secondary purification stage; and switching flow of the relativelypure hydrogen stream to the first secondary purification stage whiledesorbing the absorbed hydrogen gas from the second secondarypurification stage.
 2. The hydrogen generation method of claim 1 furthercomprising: positioning the catalytic reactor such that the temperatureof the hydrogen-rich reformate gas maintains the temperature of thecatalytic reactor.
 3. The hydrogen generation method of claim 1 furthercomprising: integrating the fuel reforming reactor with a combustionreactor that uses the off-gas stream to provide thermal energy to thefuel reforming reactor, the combustion reactor having a combustionexhaust gas at a temperature greater than 150° C.; and positioning thecatalytic reactor such that the temperature of the exhaust gas maintainsthe temperature of the catalytic reactor.
 4. A hydrogen generationmethod comprising: generating a hydrogen-rich reformate gas at atemperature greater than 150 C. in a fuel reforming reactor; separatingthe reformate gas into a relatively pure hydrogen stream and an off-gasstream in a pressure swing adsorption (PSA) hydrogen purification unit;converting carbon monoxide (CO) and at least a portion of the hydrogen(H₂) contained in the relatively pure hydrogen stream into methane (CH₄)and water vapor (H₂O) in a catalytic reactor down stream of the PSAunit; providing a first secondary purification stage downstream of thePSA unit and the catalytic reactor, the first secondary purificationstage having a water adsorbent material bed that adsorbs the H₂O; and ahydrogen absorbent (or adsorbent) material bed downstream of the wateradsorbent material bed; concentrating the hydrogen into the hydrogenabsorbent material bed; and desorbing the hydrogen from the hydrogenabsorbent material bed.
 5. The method of claim 4 further comprising:providing a second secondary purification stage downstream of the PSAunit and the catalytic reactor connected in parallel to the firstsecondary purification stage, the second secondary purification stagehaving a second water adsorbent material bed that that adsorbs the H20followed by a second hydrogen absorbent material bed; and switching flowof the relatively pure hydrogen stream to the second secondarypurification stage while desorbing the absorbed hydrogen gas from thefirst secondary purification stage; and switching flow of the relativelypure hydrogen stream to the first secondary purification stage whiledesorbing the absorbed hydrogen gas from the second secondarypurification stage.
 6. The method of claim 4 further comprising aplurality of parallel connected secondary purification stages downstreamof the PSA unit and the catalytic reactor connected in parallel, eachstage having a water adsorbent material bed followed by a hydrogenabsorbent material bed.